Supplementary fuel



July 15, 1952 M. S. ROUSH SUPPLEMENTARY FUEL Filed Spt. 10. 1948 V5.27: 0.2- 28 126. Boa 1512 E 4 WHZZ IE Patented July 15, 1952 SUPPLEMENTARY FUEL Milton S. Roush, Painesville, Ohio, assignor" to Thompson Products, Inc., Cleveland, Ohio; a

corporation of Ohio Application September 10, 1948; Serial No. 48,697-

e 1 v This invention relates to an anti-detonant type of supplementary 'fuelflfor internal combustion engines, and includes a method for preparing the fuel in stable non corrosive form. j

Specifically, this invention deal with a stable alcohol-water-oil emulsion which can contain more than 80 rnonohydric alcohol, such as methanol, ethanol ,or isopropanol, and as much as 3 cc. pergallontetraethyl lead without forming precipitates even' when' heated or exposed to oxidizing atmospheres. I

According to this invention, a detonation-inhibiting ,supplem'etary' fuel; composed' essentially of alcohol and water, and preferably also con,- taining tetraethyl 'xlead, r is rendered I stable and non-corrosive by incorporating small-amounts 'of corrosion-inhibiting emulsifiers and oils .Qr other hydrocarbons whieh are normally immiscible in the alcohol solution. It has been found that oxidation products produced by oxidation of the alcohol content. of the fuel will form slimes'and precipitates which clog filters, metering valves, and feedtubes, rendering the fuel unsatisfactory for commercial use. This oxidation is minimized by small amounts of oils either in theinhibitor or otherwise added; The oil addition is controlled to balance'the specific gravity of the inhibitor and emulsifier with the specific gravity of the alcohol-watersolution. Hydrocarbons, such as kerosene or heavier petroleum fractions having the desired specificgravity, are used for this purpose, but the total hydrocarbon content of the fuel is so insignificant that it will not"v interfere with the setting" of a c'arburetor to enrich the power fuel-air mixture delivered tothe engine even'when the antiedetonant fuel is introduced at a relatively high rat. It ispreferred-to use slightly more kerosene or other immiscible hydrocarbon than can be' rendered totally miscible with the alcohol solutign by {the emulsifier so that very minute quantities I of the kerosene tend to fioat to the top,ffor ning a thin covering 'film which additionally protects the fuel against-oxidation, r I I, I The anti-detonant type supplement'ary'fuels of this invention are immiscible with the conven tional hydrocarbon power fuels, such as gasoline, and therefore they arefed'to the engine in the form of a spray which is injected into the gasoline-air mixture ,s'uppliedtoit he, engine by the carburetor. Since engine detonatingconditions are only encountered whenthe vacuum in the engine intake manifold decreases as when the throttle valve is appreciably "opened and the engine is'operating'under-heavyload, the supple- 2'Claims. (Gigi-56) mentary fuel of this invention is conveniently fed to the engineonly whenneeded, and incontrolled amounts, by a metering device actuated by the intake manifold vacuum.

Since expensive anti-detonant agents, suclr as tetraethyl lead, areonly needed when the engine is operating under detonating conditions, the supplementary fuel of this invention contains such an agent and the main power fuel may be free from such agents; thereby effecting appreciable economies in" the" operation of the engine. Because the tetraethyl lead isonly'introduced into the engine during a small percentageof its operating cycle; deleterious; deposits of leadoxide formedin the engine by oxidation of the tetraethyl lead are minimized. I r I The fuel of this invention is preparedbyfirst dissolving the tetraethylle'adin the alcohol and then diluting the solution with a part only of the Water. The corrosion inhibitor and 'mulsifier, suchas a soluble oilcomposed of petr'oleumsodb um sulfonates of the'green'acid type, fatty sodium soaps and a glycol, is'adm'ixed with suificient kerosene to reduce its specific gravity to'about the specific gravity of the alcohol solution A small amount of water is then slowly stirredj into the kerosene-diluted soluble oil. The resulting mixture is then slowly stirred intothe leadec o'ntaining diluted alcohol'to formthe stable emulsion. If the emulsifier is first' added tothe Water-containing solution andrthe kerosene then added, stratification will occur. This procedure makes possible the retention'of'the tetraethyl lead in solution withoutvthe aid of large amounts of hydrocarbons asheretofore deemed essential! It is, then, an'object of the inventionto provide an anti-detonant type supplementary fuel form ternal combustion engines containing small amounts of corrosion-inhibiting emulsifiers for stabilizing the fuel even when used in contact with corrodiblemetals. v A further object oftheinvention is to provide an' anti-detonant-type supplementary fuel coi'n posed essentially'of alcoholand. water and stabilized with a corrosion-inhibiting emulsifier having a specific gravity balanced with thespecific gravity of the alcohol-water solution. f Another object of the invention isto are de a stable alcohol-water -oil emulsion which can 5011- tain moreftha'nBO monohydric' alcohol, asiiiiuch as-3 c'c. er'gallon tetraethyl-lead, and aflhydro carbon in an amountinsufficient to have a power fuel-value' '3' A specific object of the invention isjtoprovide an anti-detonant supplementary fuelfor internal combustion engines which is composed of 80 to 90% methanol, 10 to 20% water, up to 3 cc. per gallon tetraethyl lead, minute quantities of corrosion-inhibiting emulsifier containing fatty acid soaps, petroleum sulfonates of the green acid 7 ternal combustion engines in the form of a stable emulsion composed of from 10 to 90% monohydric alcohol containing from 1 to carbon atoms, and 90 to water, together with minute quantities of a corrosion-inhibiting stabilizer diluted with a hydrocarbon to render its specific gravity substantially equal to the specific gravity of the alcohol solution but freeifrom sufficient hydro carbon to have a power fuel-enriching effect.

. A still further object of the invention is to provide an antidetonant supplementary fuel for internal combustion engines which is composed essentially of alcohol and water but is stabilized against oxidation and heat deterioration by small amounts of immiscible hydrocarbons rendered compatible with the solution by minute amounts of a suitable emulsifier.

A further object of the invention is to provide a stable, alcohol-type antidetonant fuel by admixing a corrosion inhibiting emulsifier with a hydrocarbon such as kerosene prior to the incorporation of the emulsifier into the alcohol solution, thereby avoiding stratiflcation of the fuel.

Afurther object of the invention is to provide a method of" forming stable alcohol-type fuels with immiscible ingredients by balancing the specific gravities of the immiscible ingredients relative to the alcohol solution. I

A still further object of the invention is to provide a supplemetary fuel which is immiscible with gasoline and is composed-essentially of alcohol and water together with minute amounts of alcohol-insoluble ingredients stabilized in colloidally dispersed condition in the alcohol solution.

Other and further objects of the invention will be apparent to those skilled in the art from the following detailed description including the annexed sheet of drawings which illustrates the manner in'which the supplementary fuel of this invention is metered to the engine as needed by the engine to prevent detonation therein.

On the drawings; I

Figure l is a diagrammatic side elevational view of an internal combustion engine and fuel intake assembly equipped with a supplementary fuel injector or meteringdevice for supplying supplementary fuel of this invention to the intake manifold of the engine.

Figure 2 is avertical cross-sectional view, with parts in elevation. of the fuel injector or metering device used for supplying the supplementary fuel of thisinvention "to the engine in properly metered required amounts only when needed b the engine. I r

As shown on the drawings: I

In Figure-l a high compression internal combustion engine E is equipped with the customary air and fuel-chargingassembly including an air cleaner [0, anda carburetor I 1 receiving air from the cleaner iii. A main power fuel from the feed line 12 supplies fuel to the carburetor l l for admixture with the air to form the power fuel-air mixture. A mounting block I3 is interposed be-.

tween the carburetor II and the inlet M of the intake manifold l5 for the engine E. The atomized power fuel-air mixture from the carburetor H passes through the block I3 to the inlet l4 and is distributed by the manifold [5 to the cylinders of the engine. The conventional fan i6 is provided on the engine.

V a r A relatively small tankil'l. for the supplementary anti-detonant fuel of this invention is mounted on the fire wall [8 of the vehicle driven by the engine E.- The supplementary anti-detonant fuel is fed from the tank I! through a feed line I9 to a metering device 20 mounted on the block l3.,

The metering device 20, as best shown in Figure 2, includes a float 2| for controlling an inlet valve 22 receiving the supplementary fuel from the feed line 19. The float 2! is mounted in a float chamber 23 receiving the fuel from the inlet valve 22. I The float chamber 23 is-vented to the atmosphere at 124 and fuel under. atmospheric pressure in the neat chamber flows through a passage 25 to a diaphragm-controlled metering valve 26 andthence through a passageway 21 to a nozzle or jet pipe 28 carried by the block I 3 and opening downstream into the inlet l4. 7

The metering valve 26 has a stem portion 26a slidably mounted in a boss provided by' the float chamber-defining casing. The upper endof this stem is connected to adiaphra'gm 29 which sepa,-

rates the float chamber 23 from a'springchamber 30. The spring chamber 30 is vented by a passageway 3| to the interior'ofthe block I3 so that the spring chamber is under the influence of the vacuum existing in the inlet 14 of the engine E. A spring 32 is mounted in the spring chamber 30 andis adjusted by means: of an adjusting.

companied by decreased vacuum or increased pressure in the inlet M, the spring32 is effective to move the metering valve 26 toward open position because the decreased vacuum in the cham ber 30 is insuflicient to overcome the spring pressure. Supplementary fuel isithereupon injected in amounts determined by the, opening of the metering valve and is discharged through the nozzle 28 to comminglefwith the atomized power fuel (gasoline) and air mixture in the inlet I4. The nozzle 28 has its discharge orifice facing downstream so. that the supplementary fuel will be intimately admixed in line spray form with the main power fuel-air mixture. Of course, as the intake manifold pressure decreases to increase the vacuum in the chamber 30. likelihood of detonation decreases and the diaphragm 29 will pull the metering valve to closed position or sub: stantially closed position. h

The throttle T controls the feed of the main power fuel-air mix to the inlet [4 and, of course, when this throttle is substantially closed, the intake vacuum is high The degree of intake vacuum is therefore a function of the degree of opening of this throttle T and supplementary fuel is introduced under fullthrottle conditions under the influence of the intake manifold pressure con trolled by a linkage arrangement with the throttle valve.

In accordance with this invention, the main fuel supplied to the carburetor I I by'the feed line I2 will be free from expensive antii-detonants such as tetraethyl lead or, if. desired, can contain smaller amounts of such anti-detonants than are necessary for satisfactory operation of the engine when all ofthe anti-detcnant isifed with thepower fuel. The supplementary fuel of this invention entirely ofisets the antidetonant deficiency of the main fuel. v 1

Reference to tetraethyl lead (Pb(C2H5)4) throughout this specification and in the claims denotes the commercial product containing ethylene dibromide and ethylene dichloride in minor amounts. This commercial product, under the present Federal health laws of the United States, can only be used in maximum concentrations in fuels which are vended to the public, in amounts up to 3 cc. per gallon, and the supplementary fuels of this invention therefore contain sufficient solvents for the tetraethyl lead to prevent its con.- centration beyond the legal limits. Thus, if 3 cc. of tetraethyl lead per gallon are to be used, the supplementary fuel should-contain sufficient alcohol to dissolve this amount of tetraethyl lead. For this purpose, the fuels should contain at least 73.5% methanol, at least. 55.1% ethanol, or at least 38.5% isopropanol. Of course,-it.should be understood that lesser amounts of thetetraethyl lead could be used with fuels containing larger percentages of water. l 1 I The corrosion-inhibiting emulsifiers used for stabilizing the fuels of this invention are wetting agents which coat metal-surfaces and emulsify such immiscible materials as aqueous alcohol solutions and petroleum hydrocarbons. Fatty acid soaps, such as sodium or potassium saltsof oleic,

stearic, linoleic, and ricinoleic acids,- and rosin soaps, suchas sodium or potassium abietates, are satisfactory. These soaps conventionally contain free glycerine or other glycols which are soluble in water, and liquid at room temperatures. The preferred corrosion-resisting emulsifier, however, has the following composition expressed in-percentages by weight:

A suitable corrosion-inihibiting emulsifier of the above listed preferred type is known as Penola 2210, and is manufactured by the Standard Oil Company of New Jersey..v This material has a specific gravity of 1.05 to 1.10. 'It'can be diluted with a petroleum hydrocarbon such as kerosene to yield a mixture having a reduced specific gravity that is balanced with the specific gravity of the alcohol-water solution of the fuel.

It is preferred to dilute the corrosion-inhibiting emulsifier with sufficient lighter petroleum hydrocarbon so that the resulting diluted mixture has a specific gravity that is not appreciably more than, and preferably slightly less than, the water-alcoholsolution in which it is to be used; When these conditions are maintained, the resulting emulsion will'be stable at all temperatures including the high temperatures encoun- 6 teredunder the hood of an engine where the supplementary fuel is stored in a tank such as II. This petroleum hydrocarbon dilutedcorrosion-inhibiting emulsifier serves a three-fold function, as :follows; r

(1) Prevention of the corrosion of various metal parts in which the supplementaryffuel isstored or through which it flows en route tdthe. engine;

(2) Prevention ofthe precipitation of breakdown products of the corrosion' inhibitor;

(3) Prevention of formation-OLprecipitation products produced by oxidation of the alcohol.

The -kerosene or other petroleum hydrocarbon to be admixed with the corrosion-inhibiting emulsifiershould preferably have a specific gravity in the range from about 0.78 to about 0.81, so that the blending of the kerosene with the emulsifier in varying proportions will result in specific gravities extending over the desired range determined by the specific gravity of the alcohol-water solution. For example, if a supplementary fuel containing methanol and 15% water is desired, the specific gravity of this mixture will be 0.843, and a suitable kerosene-diluted emulsifier can be obtained by mixing 5 parts of kerosene with 1 part of the above-described Penola type emulsifienwhich has an average specific gravity of 1.07. This will yield a kerosene-soluble-oil mixture having a specific gravity of 0.845. In general, it is desirable that the specific gravity of the kerosene-emulsifier mixture lie within the range of from 0.95 to 1.05 times the specific gravity of the: desired alcohol-water solution. The specific gravity of theemulsifier. can therefore be easily controlled by controlling the percentage of the kerosene in the mixture.

The emulsifier itself is-. used,-in very minute quantities, being less 1than,1%,by weight of the fuel and preferably only about fl of 1% by weight of the fuel. The following specific example illustrates a preferred method of compounding a supplementary; fuel according to this invention composed essentially of methanol and water:"

,- a le To produce 1 gallon ofa stablesupplernentary fuel composed of about 85% by'volume of rn'ethanol, and about 15% by volume of water, 2.8 to 3.0

cc. of tetraethyl lead areadded to 0.84 to 0.86 gallon of pure methanol. The tetraethyl lead will readily dissolve in the alcohol. If the commercial 62 mix yellow *E thyl anti-knock compound is used, about 4.72 to 5.05 cc. are dissolved into the alcohol. The methanol-tetraethyl lead solution is then diluted with 0.13 gallon of water and is allowed to stand.

A soluble oil corrosion-inhibiting emulsifier of the Penola type consisting mainly of alkali metal salts of sulfonated petroleum acids of the green acid type with small amounts of fatty acid soaps, such as sodium oleate and free glycols such as diethylene glycol in the amount of 3.83 to 4.15 grams is slowly stirred into 24.90 to 25.70 cc. of kerosene having a specific gravity of .78 to .81. The emulsifier has a specific, gravity of about 1.05 to 1.10. The stirring is continued to produce a mixture of uniform viscosity. About 0.02 gallon of water is then slowly stirred into the kerosene mixture. It is important that the emulsifier be admixed with the kerosene prior to the incorporation of the water, in order to produce a stable emulsion. The uniform mixture of emulsifier, kerosene, and water is then added slowly to the alcohol solution, with constant stirring to produce the stable emulsion.

The kerosene content of Y the thus produced stableemulsion is somewhat in excess of the amount necessary for insuring the reduction of the specific gravity of the emulsifier to the specific gravity of the alcohol-water solution so as to allow for some loss through evaporation. It has been found that some of this kerosene will separate to form a very thin layer covering the top of the fuel and thereby further protecting it against oxidation; In general, the kerosene or other hydrocarbonisused within the range of from '75 to 90% by weight of'the weight'of the 'emulsifier. The kerosene-dilutedemulsifier is present in amounts equivalent to'about A of 1% by weight of the'fuel. Instead of adding all of the kerosene to the emulsifier, a mixture of 75% ker osene and 25% emulsifier can be prepared and added to the alcohol solution in an amount equivalent to about by weight of the fuel. After this addition has been completed, kerosene in the amount equivalent to about of 1% by weight of the fuel can then be added to provide the excess kerosene for insuringfhe maintenance of the'specific gravity of the emulsifier within the desired range. h

Since the specific gravity of isopropanol and ethanol is approximately the same'as the specific gravity of methanol, the above-indicated'procedures for producing the methanol-type fuel can be used to produce fuels composed of these other alcohols.

From the above descriptions it should therefore be understood that gasoline-immiscible anti-detonating supplementary fuels composed essentially of aqueous solutions of' monohydric alcohol containing'from 1 to 5' carbon atoms such as methanol, ethanol, and isopropanol,.'are rendered stable and non-corrosive by the addition of corrosion-inhibiting emulsifiers and petroleum hydrocarbons such askeros e'ne. 'Ihese fuels preferably contain 'antikno ck agents such as tetraethyl lead/The alcohol content of the fuel can vary over awide range, but'should be sufficient to maintain the tetraethyl lead in solution. Very effective fuels, according to this invention, containfrom 80 to 90% alcohol and from to 20 water, with the preferred fuels containing about 85% alcohol and about water. The preferred corrosion-inhibiting emulsifier for use with the fuels of this invention is composed of a sodium salt ofsulfonated petroleum acids of the green acid type, small amounts of fatty acid soaps and free glycols. These emulsifiers are diluted with hydrocarbons such as kerosene to reduce their specific gravity to lie within the range of about 0.95 to 1.05 times the specific gravity of the aqueous alcohol solution. -When so diluted, the emulsifiers will produce a stable emulsion. The added hydrocarbons present are in amounts insufiicient'to have any power fuelenriching effect on the main power fuel fed to the engine. In addition, the hydrocarbon will form a 'thinfilm on the aqueous alcohol solution to seal the" solution from contact "with the air; thereby further'protecting it against oxidation. The fuels of this invention are stable even at" high temperatures and will'not form slimes and precipitates heretofore encountered with the use of alcohol-type fuels.

It will, of course, be understood that variou details of the process and product may be varied through a wide range without departing from the principles of this invention and it is, therefore, not the purpose to limit the patent granted hereon otherwise than necessitated by the scope of the appended claims. Y i

.' I claim as my invention:

1. A stable anti-knock supplementary fue emulsion consisting of a solution composed of 10 to 20% by volume of water, to by volume of lower monohydric alcohol containing from 1 to 5 carbon atoms and about 3 cc. per gallon of tetra-ethyl-lead together with from to 1% by Weight of amixture consisting of a soluble oil corrosion inhibiting emulsifier containing alkali metal salts of sulfonated petroleum acids of the green acid type,-fatty acid soaps and glycols, and a sufficient amount of 'k'eroseneof a specfic gravity range between "about 0.78 to about 0.81 to reduce the specific gravity of said of sulfonated petroleum acids of the green acid type, fatty acid soaps and glycols, and-a suffi cient amount 'of kerosene of a specific gravity range between about 0.78 to about 0.81 to reduce the specific gravity of said mixture to about 0.95 to 1.05 times the specific gravity of said solution. I

MILTON S. ROUSH.

REFERENCES CITED 7 The following references are of recbifd in the file of this patent:

UNITED STATES PATENTS Number Name a Date 1,869,486 Lantz Augu2, 1932 2,316,739 Cook Apr. 13, 1943 2,404,094 Robertson July 16, 1946 2,429,707 Catalano Oct. 28, 1947 2,504,361 Van Hartesveldt Apr. 18,

OTHER REFERENCES 7 Sulphonation Products of Mineral Oil, Reuben Sperling, pages'890-897, Industrial and Eng. Chem., May 1948. P 

1. A STABLE ANTI-KNOCK SUPPLEMENTARY FUEL EMULSION CONSISTING OF A SOLUTION COMPOSED OF 10 TO 20% BY VOLUME OF WATER, 80 TO 90% BY VOLUME OF LOWER MONOHYDRIC ALCOHOL CONTAINING FROM 1 TO 5 CARBON ATOMS AND ABOUT 3 CC. PER GALLON OF TETRA-ETHYL-LEAD TOGETHER WITH FROM 3/4 TO 1% BY WEIGHT OF A MIXTURE CONSISTING OF A SOLUBLE OIL CORROSION INHIBITING EMULSIFIER CON- 